CN114438547A

CN114438547A - Electrocatalytic conjugated polymer composite material for hydrogen evolution reaction

Info

Publication number: CN114438547A
Application number: CN202210108927.1A
Authority: CN
Inventors: 邓玉婷; 程冲; 刘路畅; 李爽; 马田; 刘习奎; 周鸿菊; 马朗; 曹素娇; 周密
Original assignee: Sichuan University
Current assignee: Sichuan University
Priority date: 2022-01-28
Filing date: 2022-01-28
Publication date: 2022-05-06
Anticipated expiration: 2042-01-28
Also published as: CN114438547B

Abstract

The invention belongs to the technical field of electrochemical hydrogen production, and particularly relates to an electrocatalytic conjugated polymer composite material for Hydrogen Evolution Reaction (HER). The conjugated polymer composite material is formed by compounding a metal porphyrin coordination polymer layer and a carbon material layer, wherein the carbon material layer is formed by a carbon material with a large conjugated system, and the metal porphyrin coordination polymer layer is formed by an organic ligand with a plane conjugated structure and Ru³⁺Coordination formation; the feeding ratio of the metal coordination polymer layer to the carbon material layer is 1: 8-2: 1; ru in the metal coordination polymer layer³⁺The molar ratio to the organic ligand is 2: 1. The invention establishes a composite material with reasonable layered structure and controllable morphology on conductive carbon matrixes (KB, CNTs and rGO) with different dimensions through pi-pi intermolecular interaction, and the composite materialShows stronger alkaline HER catalytic activity than the most advanced Pt/C at present, has cost advantage and better stability, and has good application prospect.

Description

Electrocatalytic conjugated polymer composite material for hydrogen evolution reaction

Technical Field

The invention belongs to the technical field of electrochemical hydrogen production, and particularly relates to an electrocatalytic conjugated polymer composite material for hydrogen evolution reaction.

Background

As an ideal alternative to traditional fossil fuels, hydrogen energy plays a crucial role in achieving renewable and clean energy economy at its high energy density and zero carbon dioxide emissions. However, the current industrial hydrogen production route not only relies on fossil energy, but also produces a large amount of greenhouse gas CO₂. The electrolytic water process has been extensively studied in the past decade as an environmentally friendly process based on non-fossil fuels to produce low cost and high purity hydrogen. The cathodic reaction of hydrolysis can be easily promoted with the aid of an engineering effective electrocatalyst: hydrogen Evolution Reaction (HER). To date, Pt-based electrocatalysts have been recognized as "master keys" for triggering high performance HER in acidic media because of their fastest kinetics matching moderate Pt-H bonds. Unfortunately, in addition to high cost and scarcity, the catalytic activity and low stability of Pt-based electrocatalysts in alkaline media have hindered their large-scale application, prompting the search for more effective alternatives to Pt-based electrocatalysts.

Carbon-based noble metal monatomic catalysts (SACs) have excellent activity and maximum efficiency of atom utilization, and are of increasing interest in balancing electrocatalytic activity and cost. The excellent performance of the carbon-based noble metal SACs is not only derived from the unique electronic structure of noble metal atoms, the carbon matrix with larger specific surface area and high mass/charge transmission, but alsoProvides a platform for adjusting the electron density through strong intermolecular interaction, and further endows the catalyst with high-efficiency catalytic activity. Although they have wide application prospect, the widely reported annealing synthesis strategy has the disadvantages of high energy consumption, low stability, undefined nano structure, random generation of single atoms and the like. For example, in UiO-66-NH₂During the pyrolysis preparation of a single Ru-NC site catalyst, the annealing temperature is high, and a slight change in the annealing temperature will result in a significant difference in catalytic performance. In addition, in addition to the need for tight control of the annealing process, the precise elemental ratios of the precursors are also critical. In many cases, the noble metal atoms tend to agglomerate as their proportion in the precursor increases, but it is difficult to form monoatomic centers as the proportion decreases. Despite much effort in the precise design of carbon-based noble metal SACs, there are obstacles to the long-term industrial application of carbon-based noble metal SACs by means of pyrolysis.

In recent years, coordination polymer materials used in the design of carbon-based noble metal SACs have received much attention due to their tunable structure with the desired multielement composition and high surface area. For example, Sun et al (Nature Communications,2021,12(1):1369.) developed a monoatomic strategy to construct superior NiRu by introducing atomically dispersed Ru atoms_0.1-BDC HER electrocatalyst. However, the coordination polymer has poor electrocatalytic activity due to the lack of an intrinsic pi-conjugated structure having electrical conductivity, and annealing to enhance pi-conjugation may cause undesirable structural changes and even destroy fine structures, making the electrocatalytic mechanism uncertain. Therefore, there is an urgent need to obtain new thermolysis-free, structurally distinct, active site-controlled coordination polymer-based SACs to replace the expensive Pt-based alkaline HER electrocatalysts.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides an electrocatalytic coordination conjugated polymer SACs composite material for hydrogen evolution reaction, which rivets a conjugated coordination polymer layer (Ru-CPL) with an Ru-N center with good atomic scale design on a carbon substrate (namely KB, CNT and rGO) through pi-pi stacking interaction, thereby realizing high stability and high catalytic activity of the polymer layer in the catalytic field.

The conjugated polymer composite material consists of metal porphyrin coordination polymer layer and carbon material layer, the carbon material layer consists of carbon material with great conjugated system, and the metal porphyrin coordination polymer layer consists of organic ligand with plane conjugated structure and Ru³⁺Coordination formation;

the feeding ratio of the metal coordination polymer layer to the carbon material layer is 1: 8-2: 1 by weight;

the Ru in the metal coordination polymer layer³⁺The molar ratio to organic ligand is 2: 1.

Preferably, the metal coordination polymer layer and the carbon material layer are compounded by pi-pi stacking interaction.

Preferably, the carbon material is selected from at least one of carbon black, Carbon Nanotubes (CNTs), or reduced graphene oxide (rGO). Preferably, the carbon black is selected from Ketjen Black (KB).

Preferably, the organic ligand is selected from the group consisting of 5,10,15, 20-tetrakis (4-pyridyl) -21H, 23H-porphyrin.

The invention also provides a preparation method of the composite material, which comprises the following steps:

step 1, preparing the organic ligand, the carbon material, the surfactant and the acid into a solution A; preparing trivalent salt of Ru into solution B;

and 2, mixing the solution A and the solution B for reaction, and separating a solid product to obtain the catalyst.

Preferably, in the step 1, the concentration of the organic ligand is 0.31-0.33M, the concentration of the carbon material is 2-16 mg/mL, the concentration of the surfactant is 0.09-0.11 mg/mL, and the concentration of the acid is 0.08-0.12M;

and/or, in step 1, the acid is selected from hydrochloric acid or sulfuric acid;

and/or, in step 1, the surfactant is selected from PVP;

and/or, in the step 2, the reaction temperature is room temperature.

The invention also provides the application of the composite material as a hydrogen evolution reaction electrocatalyst.

The invention also provides an electrode material for hydrogen evolution reaction, which consists of the composite material and Nafion.

Preferably, the composite material is prepared by adding a Nafion solution into a composite material, the mass volume ratio of the composite material to the Nafion solution is 5mg: 9-11 ml, and the Nafion solution is prepared from Nafion and ethanol according to the volume ratio of 1: 8-10. .

In the present invention, the "Nafion" refers to a commercially available perfluorosulfonic acid resin, which is commonly used in the prior art for protection of nanomaterial electrodes, fuel cell separators, and the like, and can be obtained by direct purchase.

The invention provides a convenient layer-by-layer design scheme without pyrolysis and with low energy consumption, namely, a conjugated coordination polymer layer (Ru-CPL) with an Ru-N center with good atomic scale design is riveted on a carbon matrix (namely KB, CNT and rGO) through pi-pi stacking interaction, so that high stability and high catalytic activity of the polymer layer in the catalytic field are realized. The best Ru-CPL @ KB shows comparable or even better HER catalytic activity in 1M KOH solution than commercial Pt/C, i.e., at 10mA cm^-2Has a lower overpotential (42mV compared to 44mV Pt/C); higher TOF values and mass activities (approaching 3.83 and 8.58 times of Pt/C, respectively); 80000s stability test only drops by 30 mV. This shows that the composite material provided by the invention has very excellent hydrogen evolution reaction electrocatalytic activity.

Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.

The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.

Drawings

FIG. 1 is a schematic diagram of the assembly of Ru-CPL on different carbon substrates.

FIG. 2 is a representation of a Transmission Electron Microscope (TEM); wherein (a) Ru-CPL @ KB, (b) is a magnified view of a local region of a, (c.d) HRTEM images of Ru-CPL @ rGO and (e.f) Ru-CPL @ CNTs; (a) the inset is the corresponding average dimension, and (f) the inset is the corresponding average thickness.

FIG. 3 is a representation of a scanning Transmission Electron microscopy image (STEM) and a corresponding energy spectral x-ray spectral mapping (EDS); wherein, (a) Ru-CPL @ KB, (b) Ru-CPL @ rGO and (c) Ru-CPL @ CNTs catalysts are in STEM images and corresponding EDS element spectrograms; (d) an element signal superposition spectrogram of Ru-CPL @ KB; (e) line scan of Ru-CPL @ KB over the circled area of FIG. d.

FIG. 4 is a graph of the characterization of ultraviolet visible spectra, Fourier transform infrared (FT-IR) spectra, and XRD, wherein (a) the purple spectrum of Ru-CPL @ KB; (b) an XRD characterization pattern of Ru-CPL @ KB; (c.d) a Fourier infrared spectrum of Ru-CPL;

FIG. 5 is (a) N1s XPS and (b) Ru 3p XPS spectra of Ru-CPL @ KB and other samples.

FIG. 6 is a HER performance characterization result, wherein (a) the LSV curve of Ru-CPL @ M catalyst in 1M KOH solution; (b) the current density was 10mA cm^-2And 200mA cm^-2Comparing overpotential of time; (c) LSV curves of different thicknesses of Ru-CPL @ KB were compared to overpotentials.

FIG. 7 is a Nyquist plot of catalyst modified glassy carbon electrodes at-0.042V 1M KOH. (a) Nyquist plots of original KB, Ru-Por, optimal Ru-CPL @ KB, and 20 wt% commercial Pt/C. (b) Nyquist plots of pristine carbon nanotubes, pristine reduced graphene oxide, Ru-CPL @ CNTs and Ru-CPL @ rGO. (c) Nyquist plots of different thicknesses for Ru-CPL @ KB.

FIG. 8 is a comparison of HER performance of Ru-CPL @ KB and other materials, in which (a) is a Tafel plot; (b) exchange current density calculated using tafel plot extrapolation; (c) assuming that all Ru atoms participate in the turnover frequency and overpotential; (d) comparison of TOF and mass activity.

FIG. 9 shows the values of the mass activity of (a) Ru-CPL with different carbon groups and (b) Ru-CPL with different thicknesses.

FIG. 10 shows Ru-CPL @ KB at 10mA cm^-2Long term stability of the composition.

Detailed Description

In the following examples and experimental examples, the reagents and materials used were commercially available, specifically as follows:

ruthenium trichloride, Keqin black (Carbon ECP600JD), reduced graphene oxide (CAS: 7782-42-5), Carbon nanotubes (308068-56-6) from Aladdin. 5,10,15, 20-tetrakis (4-pyridyl) -21H, 23H-porphyrin (Por) was purchased from Soken technology. Polyvinylpyrrolidone (m.w. ═ 55000, i.e. K30, CAS: 9003-39-8), KOH, hydrochloric acid (37%) were purchased from alfa aesar. Pure water (18.2 M.OMEGA.cm) used in the experiments was from Milli-Q Academic systems (Millipore Corp, Billerica, MA, USA). Unless otherwise indicated, all reagents were of analytical grade and used as received. All aqueous solutions were prepared with deionized water (DI).

Example 1 electrocatalytic composite for hydrogen evolution reactions

The schematic material structure provided by this embodiment is shown in fig. 1. 5,10,15, 20-tetrakis (4-pyridyl) -21H, 23H-porphyrin (Por) with a typical planar conjugated structure is attached to a carbon matrix with a large conjugated system (KB, CNTs and rGO) in a mild green aqueous solution as an organic ligand, thereby reducing the surface free energy through the interaction between pi-pi molecules. Then, by Ru³⁺And the coordination self-assembly with pyridine/pyrrole nitrogen forms a completely closed Ru-N coordination polymer layer. According to the size of a carbon matrix, the obtained Ru-CPL catalysts are named as Ru-CPL @ KB, Ru-CPL @ rGO and Ru-CPL @ CNTs respectively.

The preparation method comprises the following steps:

20mg, 0.032mmol of porphyrin and 10mg of PVP were dissolved in 10mL of 0.1M hydrochloric acid solution to form solution A, followed by addition of carbon material and sonication for 30 min. 13mg 0.064mmol RuCl₃Dissolve in 10mL DI to form solution B. A is poured into B quickly and stirred for 12h at room temperature. The suspension was washed three times by DI centrifugation (11000rpm, 10min) to give the product which was dried in vacuo at 60 ℃.

Products with different carbon materials as carbon substrates were prepared according to the above method, and the specific nomenclature, the type of carbon substrate and the amount used are shown in the following table:

in the examples below, the products in the table above are given the generic name Ru-CPL. Since the carbon material KB is selected to have the best activity of Ru-CPL @ KB (1:1), Ru-CPL @ KB (1:1) is used in the following experimental examples in comparison with samples made from other carbon materials, and therefore, unless otherwise specified, the sample Ru-CPL @ KB "in the experimental examples is Ru-CPL @ KB (1: 1).

Example 2 Hydrogen evolution reaction electrode

A sample powder (10mg) of the composite material prepared in example 1 was mixed with 100. mu.L of Nafion solution (5 wt%) and 900. mu.L of ethanol in an ultrasonic bath to prepare a catalyst ink. Then 5. mu.L of catalyst ink was transferred to the GCE surface with a catalyst loading of 0.25mg cm^-2. And volatilizing the solvent to obtain the hydrogen evolution reaction electrode.

Comparative example 1Ru-Por based Polyporphyrin network

Solution A was formed by dissolving 20mg, 0.032mmol of porphyrin and 10mg of PVP in 10mL of 0.1M HCl solution. 13mg 0.064mmol RuCl₃Dissolve in 10mL DI to form solution B. Solution a was then added rapidly to solution B and stirred vigorously at room temperature for 12 h. The obtained nanoparticles were washed 3 times by deionized water centrifugation (11000rpm, 10min) and dried overnight in a vacuum oven at 60 ℃. Electrodes were made according to the method of example 2 at the same loading.

Comparative example 2Pt/C Material

Commercially available 20 wt% Pt/C (Alfa aesar), electrodes were made according to the method of example 2 at the same loading.

The advantageous effects of the present invention will be further described below by experiments.

Experimental example 1 structural characterization of Ru-CPL

The experimental example performs structural characterization on the composite material Ru-CPL prepared in example 1 and Ru-Por prepared in comparative example 1.

First, experiment method

4000-500cm by using Nicolet-560 spectrophotometer (Nicol, USA)^-1Fourier transform infrared spectroscopy analysis is carried out on Por, Ru-Por and Ru-CPL within the range, and the resolution ratio is 2cm^-1. The X-ray diffraction under Cu ka irradiation was characterized by Rigaku Ultima IV. XPS spectra were obtained by X-ray photoelectron spectroscopy (XPS, XSAM800, Kratos Analytical, UK) to examine the composition of Ru-CPL and confirm that a well-defined coordination polymer layer was successfully synthesized. Scanning Electron Microscope (SEM) images using Thermo Fisher Scientific (FEI) Apreo S HiVoc; the gold plating thickness for the Ru-CPL coordination polymer was about 1 nm. Transmission Electron Microscopy (TEM), High Resolution TEM (HRTEM), high angle annular dark field scanning TEM (HAADF-STEM), and elemental mapping analysis were performed on FEI Titan 80-300S \ TEM equipped with a Gatan EELS detector.

Second, experimental results

The morphology of the prepared Ru-CPL catalyst is characterized by a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM). The results are shown in fig. 2, where a carbon matrix with graphene surface provides a stable support for pre-assembly of Ru-CPL with Ru-N centers. Overall, the samples obtained all showed significant Ru-CPL covered layered heterostructures compared to the pristine carbon support, and no Ru-Por with bulk layered structure was observed (fig. 2 a-f).

Successful assembly of Ru-CPL on a carbon matrix was further confirmed by Scanning Transmission Electron Microscopy (STEM) and corresponding energy spectral x-ray Spectroscopy (EDS) data, with Ru, N and C uniformly distributed in the Ru-CPL (FIGS. 3 a-C). Very low but uniform Ru, N signals were detected in a further STEM-based line scan on the Ru-CPL @ KB catalyst, indicating the formation of an atomic Ru-N coordination structure (fig. 4 a-b).

In the UV-visible spectrum, the strong Soret band of Ru-Por at 417nm red-shifted to 437nm and became broader in Ru-CPL @ KB, indicating the presence of strong pi-pi interacting molecules between Ru-CPL and KB (FIG. 4 a). In Fourier transform Infrared (FT-IR) spectra, Ru-CPL @ KB is 3300cm^-1No strong N-H absorption peak appears nearby, and the characteristic peak of pyridine is 1593cm^-1Offset to 1630cm^-1Indicating that a pyridine N-Ru coordinated structure is formed (FIGS. 4 c-d). The absence of Ru particles or Ru clusters in the Ru-CPL catalyst was further confirmed by XRD results (fig. 4 b). In addition, to further confirm the chemical structure and the element ratio, X-ray was used in these Ru-CPL catalystsLinear photon energy spectroscopy (XPS). The content information of each element is shown in the following table:

first, high resolution N1s spectra were performed to investigate the presence of Ru-N coordination in Ru-CPL, and FIG. 5a shows that the binding energy in Ru-CPL is significantly shifted forward compared to that of original Por, indicating that the electronic structure has changed. This can be attributed to the transfer of electrons from Ru to N, which strongly supports the presence of a strong Ru-N coordination bond. Meanwhile, XPS spectroscopic studies of Ru 3p reveal the presence of trivalent cation Ru: ru^Ⅲ(463.44eV and 485.64eV), the Ru content in the Ru-CPL catalyst is very small, and the cost balance is good (FIG. 5 b).

EXPERIMENTAL EXAMPLE 2 HER PERFORMANCE OF Ru-CPL

This experimental example examined HER performance of the electrodes prepared in example 2 and comparative examples 1 and 2.

First, experiment method

All electrochemical measurements were performed at room temperature in a conventional three-electrode cell using a Gamry reference 600 workstation. Reversible Hydrogen Electrodes (RHE) or Ag/AgCl and graphite rods were used as reference and counter electrodes, respectively. The reference electrode (Ag/AgCl) was calibrated with RHE and the relative potential was 1.010V in 1M KOH. With an area of 0.196cm^-2As a substrate for the working electrode, a glassy carbon Rotating Disk Electrode (RDE) was used to evaluate the HER activity of various catalysts. Electrochemical experiments were performed in Ar saturated 1M KOH. All fresh electrolytes were bubbled with pure argon for 30 minutes before measurement. The RDE measurements were performed at 1600rpm, with a scan rate of 10mV s^-1。

EIS was performed using a potentiostatic EIS procedure with a DC voltage of-0.042V vs RHE, a frequency of 100kHz to 0.1Hz, a 10mV AC potential in Ar-saturated 1.0M KOH electrolyte, at 1600 rpm.

Calculation of Turnover (TOF): first, it is assumed that each ruthenium atom on the catalyst surface forms one active center. XPS was used to calculate the number of Ru atoms in the Ru-CPL catalyst and to calculate the molar mass of Ru and the mass on the glassy carbon electrodeMagnitude load (m)_Loading). Thus, TOF of Ru-CPL electrocatalyst with Pt/C is calculated from equation (1):

wherein I is LSV, and F is the Faraday constant (96485.3C mol)^-1) And n is the number (mol) of active sites. The factor 1/2 is based on the assumption that two electrons are necessary to form a hydrogen molecule.^[4]

Calculation of Mass Activity (MA): mass activity (A g)_metal ^-1) Derived from current density (MA cm)^-2) The current density was measured by mass loading (0.250mg cm)^-2) And normalization of each metal at a specific application overpotential. Equation (2) shows the calculation of MA:

wherein, | j | is the current density (mA cm) in the LSV data under a certain applied overpotential^-2) Wt.% is the mass fraction of metal in the catalyst in the XPS data.

And (3) stability testing: in a saturated Ar 1.0M KOH electrolyte, at a constant working current density of 10mA cm^-2The stability of the catalyst was tested using chronopotentiometry.

Second, experimental results

The hydrogen evolution catalytic activity of the Ru-CPL catalyst in an Ar-saturated 1M KOH electrolyte was examined. Typically by a voltage at 10mA cm^-2(η₁₀) Observed over-potential versus Reversible Hydrogen Electrode (RHE) to evaluate HER performance. As shown in FIG. 6, the LSV curve indicates that the Ru-CPL @ KB (1:1) catalyst has the highest HER activity at eta₁₀The minimum overpotential is 42mV, which is better than the commercial 20 wt% Pt/C (. eta.)₁₀44 mV). Ru-CPL @ KB at high Current Density (200mA cm)^-2) The overpotential is 216mV, which is better than that of commercial Pt/C (eta)₂₀₀348mV) and is greatly superior to the original RCatalytic activity of u-Por. It was observed by Electrochemical Impedance Spectroscopy (EIS) that the Rct values for all Ru-CPL catalysts were less than those of the original Ru-Por, which means that Ru-CPL has a faster charge transfer capability than Ru-Por (FIG. 7).

The kinetics of all samples were studied by Tafel plots. As shown in FIG. 8a, Ru-CPL @ KB exhibits a dec of 50.9mV^-1Low Tafel slope of approximately 44.1mV dec of Pt/C^-1. Tafel value of Pt/C (44.1-154.5mV dec) with increase of overpotential^-1) Increases much faster than Ru-CPL @ KB (50.9-98.3mV dec^-1) This shows that Ru-CPL @ KB has a competitive advantage in practical applications. Exchange Current Density (j) of Ru-CPL @ KB₀) Is 7.4131mA cm^-2Much higher than Pt/C (5.8883mA cm)^-2) And other catalysts (Ru-CPL @ rGO (1.9054mA cm)^-2)),Ru-CPL@CNTs(0.2831mA cm^-2) Indicating that it has excellent intrinsic HER electrocatalytic activity (fig. 8 b).

The intrinsic activity of individual Ru sites in Ru-CPL catalysts was evaluated by calculating TOF values (fig. 8 c). The result shows that the optimal Ru-CPL @ KB shows extremely high intrinsic activity, and the TOF value rises by 5.03H at the overpotential of 150mV₂ S^-1Is Pt/C (1.31H)₂ S^-1) 3.83 times (fig. 8 d). Ru-CPL @ KB shows excellent HER catalytic activity and lowest eta in all samples₁₀And a Tafel slope value.

To compare the cost of the different catalysts, the mass activity of the different Ru-CPL @ M samples was compared to the mass activity of Pt/C (FIG. 9). The optimal Ru-CPL @ KB (9.44A mg-1Ru) has a mass activity 8.58 times higher than 20% wt% Pt/C (1.10A mg-1Pt) at 150 mV. While the Ru-CPL @ KB catalyst contains only C, N and Ru, it is much less expensive than other optimal catalysts that require more noble metal in alkaline electrolyte to deliver activity.

Continuous production of H for Ru-CPL @ KB₂Stability and durability of (2) were investigated and compared with Pt/C (FIG. 10). At 10mA cm^-2At constant current density of (2), the overpotential increased only slightly by 30mV after 80000s of operation, whereas the overpotential of Pt/C shifted by 200mV after 65000 s of operation. Shows that the stability of Ru-CPL is superior to that of commercial catalysisAnd (3) Pt/C.

As can be seen from the above examples and experimental examples, the present invention provides an electrocatalytic composite material for hydrogen evolution reaction which is stable, low in energy consumption and high in catalytic activity. Through pi-pi intermolecular interaction, Ru-CPL with a reasonable layered structure and a controllable form is established on conductive carbon matrixes (KB, CNTs and rGO) with different dimensions. Under the condition of non-pyrolysis, Ru-CPL with the original structure is prepared. The Ru-CPL material provided by the invention shows stronger alkaline HER catalytic activity than the most advanced Pt/C material at present, has the cost advantage and better stability, and has good application prospect.

Claims

1. A conjugated polymer composite material, characterized in that: the composite material is formed by compounding a metal porphyrin coordination polymer layer and a carbon material layer, wherein the carbon material layer is formed by a carbon material with a large conjugated system, and the metal porphyrin coordination polymer layer is formed by an organic ligand with a plane conjugated structure and Ru³⁺Coordination formation;

ru in the metal coordination polymer layer³⁺The molar ratio to the organic ligand is 2: 1.

2. The composite material of claim 1, wherein: and the metal coordination polymer layer and the carbon material layer are compounded through pi-pi stacking interaction.

3. The composite material of claim 1, wherein: the carbon material is selected from at least one of carbon black, carbon nanotubes or reduced graphene oxide.

4. A composite material according to claim 3, wherein: the carbon black is selected from ketjen black.

5. The composite material of claim 1, wherein: the organic ligand is selected from 5,10,15, 20-tetra (4-pyridyl) -21H, 23H-porphyrin.

6. A method for preparing a composite material according to any one of claims 1 to 5, characterized in that it comprises the following steps:

7. The method of claim 6, wherein:

in the step 1, the concentration of the organic ligand is 0.31-0.33M, the concentration of the carbon material is 2-16 mg/mL, the concentration of the surfactant is 0.09-0.11 mg/mL, and the concentration of the acid is 0.08-0.12M;

and/or, in step 1, the surfactant is selected from PVP;

and/or, in the step 2, the reaction temperature is room temperature.

8. Use of the composite material according to any one of claims 1 to 5 as hydrogen evolution reaction electrocatalyst.

9. An electrode material for hydrogen evolution reactions, characterized in that: it consists of a composite material according to any one of claims 1 to 4 and Nafion.

10. The electrode material as claimed in claim 8, wherein: the composite material is prepared by adding a Nafion solution into a composite material, wherein the mass volume ratio of the composite material to the Nafion solution is 5mg: 9-11 ml, and the Nafion solution is prepared from Nafion and ethanol according to the volume ratio of 1: 8-10.